Terpene phenol resin compositions containing organophosphorus insecticides

ABSTRACT

This invention relates to pesticidal compositions, each comprising essentially one or more of certain organophosphorus pesticides intimately admixed with a terpene phenol resin of certain characteristics, the compositions being characterized by providing effective pesticidal activity over extended periods of time, even when applied as a film or in the form of small particles on surfaces and in substrates that otherwise would mask, decompose and/or promote decomposition of the pesticide, thus destroying it effectiveness.

United States Patent Roberts 1 Oct. 7, 1975 [54] TERPENE PHENOL RESIN COMPOSITIONS 3,130,120 4/1964 Schultz 424/219 3,318,769 5/1967 Folckcmer et al 424/219 X CONTAINING ORGANOPHOSPHORUS INSECTICIDES [75] lnventori Lyman Richard Roberts, Modesto,

Calif.

[73] Assignee: Shell Oil Company, Houston, Tex.

[22] Filed: Sept. 6, 1974 [2]] Appl. No.: 504,007

Related U.S. Application Data [63] Continuation-impart of Ser. No. 412,996, Nov. 5,

I973, abandoned.

{52] U.S. C1. 424/219; 424/78; 424/211; 424/212; 424/213; 424/218; 424/225 511 lnt.C1. ..A01N 9/36 [58] Field of Search 424/78, 211, 212, 213, 424/218, 219, 222, 225

[56] References Cited UNITED STATES PATENTS 2,966,440 12/1960 Gerolt .1 424/78 OTHER PUBLICATIONS Encyclopedia of Chem. Technology, Kirk-Othmer, Vol. 13, 1954, pp. 726 8c 73].

The Condensed Chemical Dictionary-8th Ed, 1971, pp. 618 & 693.

Primary ExaminerLeonard Schen kman [57] ABSTRACT This invention relates to pesticidal compositions, each comprising essentially one or more of certain organophosphorus pesticides intimately admixed with a terpene phenol resin of certain characteristics, the compositions being characterized by providing effective pesticidal activity over extended periods of time, even when applied as a film or in the form of small particles on surfaces and in substrates that otherwise would mask, decompose and/or promote decomposition of the pesticide, thus destroying it effectiveness.

4 Claims, N0 Drawings TERPENE PHENOL RESIN COMPOSITIONS CONTAINING ORGANOPHOSPHORUS INSECTICIDES This application is a continuation-in-part of applica tion Ser. No, 412,996. filed Nov. 5, 1973, now abandoned.

BACKGROUND OF THE INVENTION There are many situations where it is desirable to control insects at a locus where free movement of air ordinarily occurs, as on patios, in barns, sheds, feed lots, pens and the like, on plants and on soil. Fumiganttype insecticides are not ordinarily effective in such situations because of the difficulty in attaining and main taining an insectidally effective dosage of the insecticide; rcinfestation ofthe locus by insects usually occurs soon after the insecticide has been applied, Such ioci are best protected by applying an insecticide to one or more surfaces bounding, or within, the locus to be protected from insects. To prevent rapid reinfestation, it is necessary to use an insecticide having a long residual life. However. the use of residual insecticides, such as chlorinated hydrocarbons, is currently in disfavor, due to the alleged buildup of such insecticides in the envi ronment and in animal tissues.

Various organophosphorus insecticides are well known for their high activity in controlling insects. In general, such insecticides are non-residual, being bydrolytically unstable and/or volatile, and do not build up in animals or the environment, thus presenting fewer environmental problems.

In particular, volatile beta-halovinyl phosphate insecticides are well known for their outstanding activity in controlling insects within an enclosed locus or when placed in a position next to the object to be protected. These volatile pesticides need present no environmental problems because they can be formulated to be released to the environment in quantities that are harm less to animal life but toxic to insects. Moreover, these compounds are rapidly metabolized or broken down in an animal body into relatively harmless substances leaving no accumulated residue in body tissues.

However, it is often difficult to exploit the inherent effectiveness of organophosphorus insecticides.

a. Many tend to be sensitive to water. such as mois ture in the air or soil, decomposing hydrolytically to inactive materials.

b. Many are sensitive to surfaces on which they are applied,

i. some surfaces tend to promote their reactivity to water; and

ii. some surfaces (particularly in soil) cause their decomposition,

'. Some surfaces tend to mask the effect of the insecticide, absorbing or adsorbing it, so that it is not available to insects. Soil may also have this effect.

d. Some ofthe most effective insecticides for controlling flying insects, such as flies in and around houses, barns, sheds, pens and feed lots and/or on animals, are so volatile that it is very difficult to maintain them at a locus to be protected for long enough time for them to be effective against the insects.

e. Most are quite toxic, requiring special handling techniques to avoid injury to the person applying them, or others working in the area where they have been applied.

To overcome these drawbacks and realize the inherent effectiveness of these insecticides, it is known to incorporate them in resin matrices, from which they slowly and continuously pass to the surface, becoming available in amounts which control the insects but are non-toxic to humans and warm-blooded animals,

Typical compositions of this kind are disclosed in US. Pat. Nos. 3,318,769, 3,076,744 and 3,223,513 and Canadian Pat. Nos. 701,470 and 755,683,

Broadly speaking, for a resin to be suitable for this purpose, it must have the following characteristics,

1. It must not cause degradation of the insecticide:

2. It must be physically compatible with the insecticide that is. it must readily mix with the insccticide to form a stable, uniform (molecular) dispersion of the insecticide throughout the resin matrix, from which dispersion the insecticide does not separate spontaneously as a pure separate phase as by syneresis, or when subjected to pressure (eg, when the composition is squeezed),

3 It must protect the insecticide from the effects of water (condensed moisture, moisture in the air, wash water, water in formulations, etc, the composition made from the resin must be chemically and physically stable to moisture: it must be non porous and hydrophobic; it must provide this protection when the composition is applied as a film or as small particles;

4. It and compositions made from it must be stable with respect to surfaces to which the are applied and must protect the insecticide from any ad erse effect the surface might have; they must provide this protection when the composition is applied as a film or as small particles;

5. Compositions made from it must be easy to formu late into formulatitms having any desired physical shape or condition; such a composition must be capable of being formulated as a solution suspension, emulsifiable concentrate, or other liquid formulation, or as a powder, dust or other particulate formulation, to give the desired form (film, droplets, particles) on the surface to which it is to be applied;

6. Compositions made from it must control evolution of the insecticide from the body of the composition to its surface, where it is available to control insects, only at the rate necessary to provide such control; it must do this even though the composition is in the form of a thin film or small particles.

Prior art compositions are not suitable for applications in which they are used in a form having high area to-volume ratios, as in films or small particles, failing to meet criteria (3), (4) and (6). They provide the necessary insecticide release rates and protection for the insecticide when the composition is in a form having a low area-to-volume ratio, but release the insecticide much too rapidly and fail to protect it from moisture and/or the effects of surfaces when the composition has a high area-to-volume ratio. Accordingly, such compositions are not suitable for controlling insects at loci which are not enclosed and/or through which air is free to circulate.

Also, such compositions are not suitable for applica tion to crops and other plants, or to soil, where the composition is on the plant or on and/or in soil in the form of a film or small particles.

DESCRIPTION OF THE INVENTION It has now been found that terpene phenol resins having certain characteristics are uniquely superior as the resin matrix for extending the effective life of certain organophosphorous insecticides, releasing the insecticide at useful rates and protecting it from the effect of moisture and/or surfaces even when the resin/insecticide composition is in a form having a high surface-to volume ratio, as in films or small particles.

Since mixtures of these insecticides, as well as single species thereof, are contemplated in the invention. the term insecticide'- as used herein include mixtures of the defined insecticides, as well as the individual insecticides.

The organophosphorus insecticides contemplated in this invention are organophosphates and their sulfur analogs of the following formulae (classes):

wherein each R, which may he the same or different, represents alkyl of from I to 10, preferably 1 to 4, carbon atoms, X is oxygen or sulfur, Y is hydrogen or middle halogen (i.e., Cl .or Br), Z is hydrogen or alkyl of from one to four carbon atoms, hal" is middle halogen, and n 2 or 3.

Typical, exemplary species of the formulations ofthis invention are set forth hereinafter in this specification. Certain classes of organophosphorus insecticides are of particular interest in this invention. Activity, volatility and hydrolytic stability vary from class to class, even from species to species. In the present invention. some respond more favorably and exhibit longer effective life than others, in that their residual activity is extended more by formulation with resins of this invention. In no case is the residual activity of any of the classes or their members lessened by formulation with such resins, and in most cases the residual activity is considerably en hanced thereby, In all cases. the insecticide is protected from adverse moisture and/or surfaces and safety in handling it is provided.

The classes of organophosphorus insecticides of particular interest are as follows:

a. Compounds of class (4) above, typical species of this class being:

01 Z-chloro-1-(2,5-dichlorophenyl)vinyl] (IO-diethyl phosphorothioate; the corresponding dimethyl ester; Z-chlorol 2,4,5-trichlorophenyl )vinyl dimethyl phosphate; the corresponding diethyl ester; and Z-chlorol 2,4-dichlorophenyl )vinyl diethyl phosphate; the corresponding dimethyl ester; 1). Compounds of class (3), typical species of this class being;

l,Z-dibromo-2,2-dichloroethyl dimethyl phosphate. 1'. Compounds of class (5). typical species of this class being:

2-( wmethylbenzyloxycarbonyl l -methylvinyl methyl phosphate. d. Compounds of class (9), typical species of this class being:

dimethyl ate. 6. Compounds of class (I), typical species of this class being:

2,2-dichlorovinyl dimethyl phosphate. O-(lZ-dichlorovinyll 0,0-dimethyl phosphorothio ate.

hlorovinyl diethyl phosphate. -dichlorovinyl methyl octyl phosphate.

trichloro- 1 -hydroxyethylphosph0n- Of particular interest are the compositions of this invention wherein the insecticide is a beta-halovinyl dialkyl phosphate i.e., class l), a supra, especially the subclass wherein X is oxygen. Because of its characteristics, the most preferred species of this subclass is 2,2 dichlorovinyl dimethyl phosphate, commonly known as DDVP.

Also of particular interest are the compositions wherein the insecticide is ofclass (4), especially the subclass wherein each R is methyl or ethyl, X is oxygen and Y is hydrogen, n is 2 or 3, and hal is chlorine.

The resins contemplated as the matrices in this invention are terpene phenol resins having a softening point (ring and ball method) of 100C or higher and a phenolic hydroxyl value of about 0.14 equivalent per 100 grams of resin, or higher, measured by the procedures outlined by Kucharsky and Safaric in Titrations of Non-aqueous Solutions", Elsevier, 1965, pages 216 and 217, Methods C & D. It is preferred that the softening point be above about 120C and the phenolic hydroxyl value be about 0.2 equivalent per [00 grams of resin.

These terpene phenol resins, which themselves are well known in the art, are generally pale, hard, thermoplastic friable resins and are the resinous condensation products of a terpene and a phenol, typically a monoor bicyclic monoterpene hydrocarbon and a monocyclic monohydric phenol. They may be prepared by reacting various terpenes, such as dipentene, a-pinene, limoncne and various turpentine cuts comprising predominantly these and/or other monoor bicyclic monoterpene hydrocarbons with phenols, such as phenol, cresol, alkylated phenols, for example normal butyl phenol, tertiary butyl phenol, propyl phenol and the like in the presence of an ionic or condensation catalyst such as sulfuric acid, a sulfonic acid, aluminum chloride, boron trifluoride, or the molecular compounds of boron trifluoride with ethers, acids, alcohols and phenols as disclosed in US. Pat. No. 2,343,845, to which express reference is hereby made, see also Kirk- Othmer, Encyclopedia of Chemical Technology, First Edition, Volume 13, pages 725-6, to which express reference also is made. These terpene phenol resins which are employed in the compositions of the pres ent invention are soluble in a variety of organic solvents and have varying degrees of solubility in hydrocarbon solvents. Suitable terpene phenol resins may be prepared by reacting as much as 5 parts of the terpene or mixture of terpenes with one part of the phenol, although lower proportions, bcaring in mind that the hydroxyl value of the resinous product will be a function of the ratio of terpene to phenol employed and that this ratio should be adjusted, as can readily be ascertained by those skilled in the art, to yield a resinous product having the desired hydroxy value. Particularly suitable are the terpene phenol resins sold under the tradename NIREZ Series 2000 Resins, by Newport Division of Reichhold Chemicals, Inc.

As has already been pointed out herein, one of the principal shortcomings of the prior art matrices has been the fact that when the final composition is used in the form of a film, or as small particles, having a high area-to\'olume ratio, they release the insecticides too rapidly. It appears that in such compositions, movement of the insecticides from the body of the composition to its surface is solely by diffusion. and this mechanism would predict increase in release rate with increase in the area-to-volume ratio, provided the insecticide does not build up on the surface of the composition. in the case of the prior an compositions, once at the surface, the insecticide apparently is free to leave. if volatile, it vaporizes substantially at the rate it appears at the surface. If solid, it merely lies on the surface, free to be removed by contact with the insect, or some physical force such as vibration, rubbing, or the like.

However, in the case of the terpene phenol resin compositions of this invention, release of the insecticide does not appear to be controlled by diffusiosn alone, the release rate being much slower than would be the case if it were only diffusioncontrolledd. Thus, when a volatile insecticide such as DDVP is mixed with such a resin, the vapor pressure of the insecticide in the mixture is much lower than that which would be expected from Raoults law for a simple solution of the insecticide in the resin. Even in a fresh deposit of a resin/DDVP mixture, which may be quite soft because of the relatively low resin/DDVP ratio, the escaping tendency of the DDVP is low; as DDVP escapes, the deposit hardens and the escaping tendency of the DDVP is further reduced.

Apparently, the insecticide and resin interact by hydrogen bonding to form a complex, with the mixture being at equilibrium between complex at the surface and complex within the body of the composition. When the insecticide/resin composition is exposed to the at mosphere or to an aqueous medium, exposing complex on the surface of the composition, reaction occurs, hydrogen bonds breaking and freeing molecules of the in secticide. These free insecticide molecules then are available for controlling insects. Then inevitably such free insecticide molecules are lost from the surface of the composition: by contact with an insect and/or by vaporization if the insecticide is volatile, or as the result of mechanical forces (vibration, rubbing or the like) if the insecticide is an essentially non-volatile liquid or solid. Loss of the molecules of free insecticide appears to disturb the equilibrium causing breakage of hydrogen bonds in complex in the body of the composition to yield molecules of free insecticide which then migrate by diffusion to the surface where they form complex to re-establish the equilibrium.

The rate at which free insecticide molecules are made available at the surface of the composition thus appears to depend upon three factors: (a) the rate at which complex at the surface of the composition is broken down; (17) the rate at which hydrogen bonds in complex in the interior of the composition break; and (c) the rate at which free insecticide molecules diffuse from the interior to the surface of the composition. The rate at which complex at the surface reacts appears to be relatively slow; so does the rate at which hydrogen bonds in complex in the interior break. Further, since the terpene phenol resin matrix is a hard, highly viscous organic glass, the rate at which molecules of free insecticide diffuse through the resin is relatively slow. As a result of these three factors, the rate at which free molecules of the insecticide are made available to control insects is much slower than the rate provided by prior art compositions. Accordingly, the resin compositions of this invention are suitable for use in the forms of films or small particles whereas the prior art compositions are not.

However. whatever the reason or mechanism involved. the terpene resin compositions release the in secticide at desired rates when in a form having a high surface-to-volume configuration tie. film or small particles) as well as when in a form having a low surface to-volume relationship. Accordingly. these new com positions enable efficient utilization of the insecticide in situations wherein the prior art compositions cannot be used.

The second significant shortcoming of prior art resin compositions is the fact that. when in a form having a high surface-to volume ratio. they do not protect the insecticide from moisture and from the adverse effects of surfaces to which the composition is applied. In contrust. the resin compositions of this invention protect the insecticide under such conditions. The resins readily mix with organophosphorus insecticides to form what appear to be essentially uniform dispersions of the molecules of the insecticide las the complex) in the resin. The resin matrix itself is a highly viscous organic glass which is stable to water. It and the insecticide compositions prepared from it are hydrophobic. so that the composition is not wet by water, nor is it soluble in. or permeable to. water. Since the resin/insecticide complexes appear to be relatively stable to moisture and to the effect of surfaces on which the composition is applied. these resins protect the insecticide from the adverse effects of moisture. even when in a form having a high surface-to-volume ratio.

Otherwise. the tcrpene phenol resins meet all of the criteria set out above for a useful resin matrix. The resins themsches do not cause degradation of the insecti cide. The resin compositions do not react with surfaces which they contact. and protect the insecticide from any adverse effect that such surfaces might have upon the insecticide lhe compositions of this invention thus meet all of the criteria for a practical. useful composition for prolonging the effcctive life of an organophosphorus insecticide. even v. hen the composition is in the form of a film. small particles. or other form having a high area to-volume ratio.

The compositions of this invention can he prepared and formulated in a number of ways and applied by a variety of techniques: they can be formulated as (l J \vater-emulsible or dispcrsil lc concentrates. in which the composition is confined with a suitable emulsifying or dispersing agent; optionally. the formulation can contain a suitable solvent for the composition; (2) liquid based sprays containing an organic solvent or niixture of soIvents; 1 3| aerosols; (4) baits containing an attractant such as food. or a pheromone; (5} dusts. ponders or granules. It is thus evident that the compo sition alone can he applied to control insects. or the composition plus any desired other material or materials can be used.

A composition of this invention can he used to kill insects by applying the composition to a locus that the insects will contact. or closely. approach. in the case of a volatile insecticide. Thus the composition can he ap plied to a surface to protect that surface from attack by insects or it can he applied to a surface bounding or located within an area or volume to be protected. The compositions can he used on any common surface, such as wood. metal. cloth. concrete. plaster. etc. commonly associated with fences and such buildings as pens. sheds. barns. houses. and the like. where common insect pests are a problem. The compositions can also be sprayed or dusted on animals. crops, etc. and can be used in or on soil. Further. it has been found that the compositions may be applied to water to control insects. for example. mosquito larvae. therein. Also. since some of the organophosphorus insecticides conternplated by the invention are known to be effective anthelmintics for controlling parasites in the gastrointestinai tract of warm blooded animals. compositions of such anthelmintics according to the present invention can be used to control parasites in warm-blooded animals 7 for example. a composition can be administcred in the food and/or drinking water of warmhlooded animals, such as domestic animals. pets and animals grown for their fur or hide and/or meat.

One convenient way to formulate the resin/insecticide composition is to bring the resin and insecticide together in a mutual solvent and maintain that solution until the composition is to be applied. or if used to form a powder. by spraying such a solution into a chamber to effect volatilization of the solvent and collecting the resulting powder or dust.

In some cases. the ingredients can simply be mixed to form the composition, which then can be converted to the desired physical shape and form.

When used as dusts. the compositions can be applied as with sprays or may be used in dust bags. Both dusts and granules may be used in baits. placed in areas or passageways known to be used by insects. or applied to or into soil for the control of soil-dwelling insects. or introduced into water to control insects therein. or into the feed andtor water of vvarm-blooded animals to control internal parasites.

Solutions useful for spraying can be prepared using any of the well-known inert pesticidal solvent carriers or mixtures thereof. Examples of such carriers include petroleum fractions of intermediate viscosity and volatility such as kerosene. diesel oil. coal tar oil and other light mineral oil distillates. Oils of animal and vegetable origin may also be used as may hydrocarbons such as toluene. xylene. naphthalene. and alkylated naphthalenes. Other organic liquids of appropriate volatility such as alcohols. ketones and chlorinated hydrocarbons may also be useful. Examples of organic solvents include cyclohexanol. cyclohexanone acetone. methyl ethyl ketone. methylene chloride. tetrachlorethane. trichloroethylcne. and tri and tetrachlorohenzene. In some cases. mixtures of these solvents may be found to be superior to the individual solvents.

In general. it will be found desirable to use a solvent that is relatively highly volatile. When a droplet of the resin/insecticide composition is a solvent. i.e., a solution. is deposited on a porous or rough surface. it is mo bile and can penetrate such a surface. The amount of the resin/insecticide composition remaining at the sur face where it is most effective. depends upon (and is roughly inversely related to) the depth the droplet penetrates. The degree of penetration tends to be less (and the surface deposit more I the more volatile the solvent. During passage between the sprayer and the surface. and before penetration into the surface. the solution loses some of the solvent by evaporation, the liquid vol ume of the droplet decreasing. and the fluidity of the composition decreasing. reducing the penetration of the solvent into the surface. Therefore, the greater the solvent volatility. the higher the surface deposit. For this reason. and because oftheir ready availability. light aromatic solvents such as benzene. toluene. the xylcnes and other alkyl benzcncs are among those preferred.

Of course. liquids that are not solvents for the insecticides may be used to advantage in some applications either alone or in combination with one or more sol vents and/or other adjuvants as disclosed herein.

in the preparation of sprays. whether solvent based on emulsifiablc concentrates. it may be desirable and even necessary to add adjuvants such as a spreading. wetting. emulsifying or dispersing agent. Materials that can be used may be non-ionic. anionic or cationic such as fattyacid soaps, rosin salts. saponins. gelatin. casein. long-chain fatty alcohols. alkylaryl sulfonates. longchain alkyl sulfonates. ethylene oxide condensates. long-chain amines and ammonium salts, phosphate ester complexes and the like. Typical non-ionic products include condensation products of aliphatic alcohols. amines and carboxylic acids with ethylene oxide. Examples include polyoxyethylcnc sorbitan monolaurate. -monoolcatc. -tristearatc. and -trioleate: octyl phcnosy polyethoxyethanol; and oleylamine ethylene oxide condensate.

Anionic products that may be used are the free acids of complex organic phosphate esters. the sodium salt of dodecylbenzenesulfonic acid. petroleum sulfonatcs such as sodium lignosulfonatc and sodium lauryl sulfonate.

Cationic products such as quaternary ammonium compounds. e.g.. alkyl pyridinium halide and alkyl ammonium halides may also be used.

The weight ratio of resin to insecticide in the compositions of this invention will normally vary from about 111:1 to (1.3:1 with ratios of about 8:1 to 1:] being pret'errcd for insect control. For use as anthelmintics. a resin/insecticide weight ratio of from about ().4:1 to about 1:] will be found to be suitablev in normal use formulations of the compositions of this invention. prior to application. may contain an insecticide content of from as low as about (1.1% by weight to as high as is practical. Generally the upper limit need not surpass about 70% by weight. The resininsecticidc composition can be shipped as a concentrate in an organic solvent along with any desired adjuvants and then diluted with water if used as an emulsifiablc concentrate or with additional solvent as desired for spraying.

Concentrates will normally contain about 457()f 2 by weight of the resin/insecticide composition dissolved in about 28-5 3% of an organic solvent and additionally containing from about 2 to HV/r'w of an emulsifying or dispersing agent.

The formulations may be applied with conventional spray equipment.

Because of the slow release of the insecticide. sur faces that have been treated according to the invention remain to\ic to insects thereon over an extended period of time. which may vary depending upon climatic conditions such as temperature and humidity. lnsccticide/resin compositions of this invention have remained acti\ c over a period extending from a few days to se\eral months. As previously explained these conr positions are resistant to hydrolysis when the surface becomes wet by humidity. rain. hosing down of ham walls. ctcv Similarly. compositions of this invention when applied to water slowly release the insecticide to control insects in the water. and when administered bl I orally to a warm-blooded animal. slowly release the insecticide to kill worms in the gastro-intestinal tract.

Additional advantages which may be attributed to this invention lie in their safety. The resin enables application of an effective dosage of an insecticide without hazard to persons or animals in or about a locus to be protected the composition releases the insecticidc at a rate which effectively kills insects. but which is so slow that the amount of free insecticide available for contact by a person or animal at a given moment is not toxic to the person or animal. Thus acute dermal toxicity studies on rats utilizing DDVP as the toxic-ant showed that the terpene phenol resin decreased the dermal toxicity of DDVP by about tenfold.

The compositions of the present invention are effec tive in the control of all invertebrate pests which organophosphorus pesticides are generally known to Control. While these pests are generally referred to as insects" they are inclusive of other invertebrate pests which are not true inscctrf' but are commonly designated as such. Thus the compounds of this invention may be used in the control of flies. mosquitoes. moths. worms. caterpillars. weevils. beetles, ticks. mites, spiders. cockroaches and the like. Also, the compositions may be used to control endoparasitic helminths which certain of the organophosphorus insecticides of this invention are known to control.

if desired. the compositions of this invention can include other ingredients such as dycs pheromones. baits and the like. Also mixtures of one or more organophosphorus insecticides may be used as may mixtures of an org;inophosphorus insecticide and other insecticides. or pesticides such as herbicides.

The invention is illustrated by the foliouing cxam plcs:

EXAMPLE I A B (oniponent '1 \\t r t DDVP U75 (1 75 NIREZ Itil)" l 25 (will! Methylene chloride NI UH 55.25 l.l.l-trichlorethanc 33 (Ill I) (It) liill) |5oil Hydrocarbon propellant 'lev ene henol resin, oitl by the feu oit |]t\l l\l1'l ol Rcithlioitl (in-manti inc wl'lcnnig point tnng and ball method) about llI( phcnohc hydroul \aluc approximately 1 IE ctmnalenl per lot! gtiit1is molecular ttglll, tIPtHHHIlMlItI} (71H.

55M \sobnlnnt. 4*"1 pro ane EXAMPlt. ll

A composition suitable for use as a scatter bait insec ticidc was formulated by blending together the following components in the amounts indicated:

('onipoucnt 1 wt l)l)\l U 55 lerpcnc lhcnol Resin tNlRt-l/ 2H1) lit! ()1! Red l) o ol [)icalite 47b idiatoniaceous earth 1 1 (iii Coarse granulated sugar 94,44

EXAMPLE III The bait composition of Example II was tested by placing 50 mg samples of bait in uncovered petri dishes and periodically placing the uncovered dishes in 1 cubic foot wire cages containing 100 flies for a 24 hour period. The temperature was maintained at 80F, ordinary room humidity. A milk sop was provided for food for the flies. The number of dead flies was counted at l, 3, S and 24 hour intervals after introduction of the sample into the cage as indicated in Table I.

EXAMPLE lV Compositions suitable for use as emulsifiablc concentrates were formulated by mixing together the ingredients in the following proportions.

' hee autl ol' co|np|e\ organic pho phate e ter EXAMPLE V Plywood panels (4 it each) were brush coated with lime whitewash and allowed to dry under ambient conditions for two days. The compositions of Example lV-l) and lV-r were diluted with water to form an emulsion containing 1)? DDVP. Duplicate panels for each sample were sprayed with the emulsion so that each contained 50 mg DDVP/ft of panel. After drying under ambient laboratory conditions the panels were removed from the laboratory and placed in a large open lath house. One set from each sample was placed so that the panels received direct sunlight through the laths covering the roof of the building. A second set was placed under some tables in the building so that the panels received very little direct sunlight. The panels were returned to the laboratory at weekly intervals for testing against house flies. Two replicates of 25 house flies (MUA'CU domcsticu) in screened cages were placed on each panel and exposed to the surface continuously for 24 hours. Milk pads were placed on the screen cages for food during exposure. At the end of the 24 hour exposure period fly mortality counts were made with the results set out in Table ll.

EXAMPLE v1 Plywood panels were whitewashed as in Example V. Duplicate sets of Portland cement concrete blocks and whitewashed panels of 36 in area were sprayed with water diluted emulsions of Exaples lV-b and lV-a' containing 1% DDVP. The areas sprayed contained about 100 mg/ft of DDVP. After drying for one day 25 house flies (Mm-ca domas'rit'cl) in screen cages were placed on the blocks and panels. A milk pad was placed on the cages for food. After 24 hours of exposure the cages were removed and the number of dead flies counted. The blocks and panels were maintained in a small room at -88F and 85 9071 relative humidity. The blocks and panels were removed from this environment at intervals and tested in the laboratory as described in Example V.

The results of testing are set out in Table Ill.

EXAMPLE Vll Plywood panels were whitewashed as in Example V. Duplicate sets of Portland cement concrete (PCC) blocks and whitewashed (WW) panels of 36 in area were sprayed with water diluted emulsions of various organophosphorus insecticides as given in the table below. The areas sprayed contained about 50 mg/ft of the insecticide. Table IV reports the results. The undiluted formulation of each insecticide is given. The resin used was NlREZ 2019. Unless otherwise indicated, the solvent was xylene. The emulsifier was GAFAC RE 6H).

The insecticides tested were:

l. Malathion, S-[ l,2-di(ethoxycarbonyl)ethyl] dimethylphosphorothiolothionate (Class 2), as a commercial technical product, purity unknown.

2. Naled, dimethyl l,2dibromoQQ-dichloroethyl phosphate (Class 3), as a technical product, 92% naled, 0.57: DDVP.

3. SD 30040, O-(2,2-dichlorovinyl) 0,0-dimethyl phosphorothionate (Class I as a technical product, 9471 SD 30040, l.4 /r DDVP.

4. Methyl parathion, 0,0-dimethyl O-p-nitrophenyl phosphorothioatc (Class 8), as a technical product, 80?! methyl parathion.

5. Chlorfenvinphos, 2-chlorol 2,4-

dichlorophenyl )-vinyl diethyl phosphate (Class 4), as a technica product, 9571 beta and alpha iso mers, l0:] ratio) 6. Crotoxyphos, l -methylbenzyl 3- (dimethoxyphosphinyloxy )-cis-crotonate (Class 5 as a technical product, 8571 crotoxyphos.

7. Dichlorvos (DDVP), dimethyl 2,2-dichlorovinyl phosphate (Class as a technical product, 96.57: DDVP, l'il trichlorphon.

8. Dim ethoate, 0,0dimethyl S-( N- methylcarbamoylmethyl )-phosphorodithioatc (Class 6), as a commercial technical product, 95% dimethoate.

9. Monocrotophos, cis-3-( dimethoxyphosphinyloxy N-mcthylcrotonamide (Class 7), as a technical product, 81 .8/( monocrotophos.

l0. Mevinphos, Z-methoxycarbonyll -methylvinyl dimethyl phosphate (Class 9), a technical product, 65.3% alpha isomer of mevinphos.

EXAMPLE Vlll on An emulsifiable concentrate of mevinphos was prc- 0 pared as follows: T T

240 g of PHOSDRlN Insecticide (6371 alpha-isomer of mevinphos), 360 g of Nirez 2019 and 80 g of (hal),, GAFAC REfilU were mixed with sufficient xylene to form 1 liter of the mixture Portions of this emulsible concentrate (hereinafter designated as Formula A) were diluted with different amounts of water and the resulting mixtures were sprayed on potted cotton plants, which then were held at ambient conditions. At intervals thereafter leaves lc d of =c were removed and infested with houseflies in a l screened petri dish supplied with food for the flies. The R( effect of the toxicant on the flies were noted after 24 hal ) R -O O (T hours exposure, At intervals. leaves were removed, (m their stems placed through holes in small platforms into Rio 5 beakers of water and the leaves were infested with com l carworm larvae. The effect of the toxicant on the larwe was noted after 48 hours exposure. For compari RTO son. a commercial cmulsible concentrate formulation O 0 H of mevinphos containing no resin (heremafater desigl1 nated as Formula B) was tested in the same way. The =CH results are summarized in Table V. R-() CH Z TABLE V Percent mortality of test insect lest in contact with leaves of indi- Noi Formula Dosage" cated age (hours) after spraying Houseflies Corn Earworms u 4 24 as n 4 24 As B 025 85 3 u o 0 It] 0 u 2 B 050 ss 36 2 4 50 3o 20 u 1 a ion 74 9 70 7o 20 4 A I) 2% 100 54 an 72 so so 50 s A mo 96 no So so 70 r A in 100 100 lot) as so an 71) so 7 None-Control (J l (I Pounds ol .lclhe Ingredient per acre What is claimed is:

1. An insecticidal com osition com risin 'm insectip p g l-:P N01 cldally effective amount of an organophosphoius com- 45 pound selected from the group consisting of:

and

in R-0 (9y R-O 0 o wherein each R, which may be the same or different.

RO V is alkyl of from one to four carbon atoms, X is oxygen \fi or sulfur. Y is hydrogen or middle halogen. Z is hydro- P SCH"C"OVR gen or alkyl from one to four carbon atoms "hal" is l middle halogenand n is 2 or 3, in intimate admixture 6U with a tcrpene phenol resin having a softening point of at least 100C, a phenolic hydroxy value of from about ()l 14 to about t).2l equivalent per IUU grams of resin and a molecular weight of about 620, the eight ratio l3) R" o 0 of resin to insecticide being in the range of from about 6g Szl to about l:l.

P lull! 2. A composition according to claim 1 wherein the ml insecticide is one having formula (I). each of R is methyl, X is oxygen, "hal" is chlorine and Y is chlorine and the resin has a softening point of about l22C. u phenolic hydroxyl value of about 0.2l equivalent per 100 grams of resin, and u molecular weight of about 620.

3. A method for protecting a locus from insects which comprises providing at said locus on lflSCCIiCid 

1. AN INSECTICIDAL COMPOSITION COMPRISING AN INSECTICIDALLY EFFECTIVE AMOUNT OF AN ORGANOPHOSPHOROUS COMPOUND SELECTED FROM THE GROUP CONSISTING OF:
 2. A composition according to claim 1 wherein the insecticide is one having formula (1), each of R is methyl, X is oxygen, ''''hal'''' is chlorine and Y is chlorine, and the resin has a softening point of about 122*C, a phenolic hydroxyl value of about 0.21 equivalent per 100 grams of resin, and a molecular weight of about
 620. 3. A method for protecting a locus from insects which comprises providing at said locus an insecticidally effective amount of the composition of claim
 1. 4. A method for protecting a locus from insects which comprises providing at said locus an insecticidally effective amount of the composition of claim
 2. 